CN105657877B - Super stretchable graphene Electric radiant Heating Film of one kind and preparation method thereof - Google Patents
Super stretchable graphene Electric radiant Heating Film of one kind and preparation method thereof Download PDFInfo
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- CN105657877B CN105657877B CN201610049453.2A CN201610049453A CN105657877B CN 105657877 B CN105657877 B CN 105657877B CN 201610049453 A CN201610049453 A CN 201610049453A CN 105657877 B CN105657877 B CN 105657877B
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- graphene
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- heating film
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
Abstract
The invention discloses a kind of super stretchable graphene Electric radiant Heating Films and preparation method thereof.The Electric radiant Heating Film is woven by the graphene fiber with helical structure, the fiber not only elongation at break with superelevation, and realizes that preparation method is simple, specially to the quick response of 30 DEG C 420 DEG C of high temperature at safe voltage 0.5V 5V:Graphene film will be thermally treated resulting in after graphene oxide membrane electronation in 500 3000 DEG C of high temperature furnaces, then uniformly obtains graphene fiber after winding.Graphene Electric radiant Heating Film is obtained after graphene fiber is woven.Graphene Electric radiant Heating Film has the rate of heat addition and rate of temperature fall of superelevation, the temperature-responsive of superelevation, and operating voltage is relatively low, it can be used for human body, it is used as human body electrothermal cloth, and since performance can be drawn high, adapts to physical activity in use, such as muscle stretch, therefore intelligent electric-heating material extensive use can be used as.
Description
Technical field
The present invention relates to a kind of super stretchable graphene Electric radiant Heating Films and preparation method thereof.
Background technology
Grapheme material causes whole world scientists widely to be studied, the Univ Manchester UK strong of peace moral in 2004
Jim and Constantine Nuo Woxiao loves professor are because the initiative experiment on two-dimensional graphene material obtains promise in 2010
Bell's Physics Prize.Graphene shows abundant chemical property, can be surface modified by different chemical reactions,
Obtain a series of chemical derivatives.Graphene has high fracture strength and Young's modulus, electric property excellent.Grapheme material
It is excellent heat conduction and thermo electric material.Traditional thermo electric material such as nichrome, there are of high cost, density is big, quality weight and processing
The shortcomings of complex process, cannot stretch during use, and graphene fiber flexibility is good, and the rate of heat addition is fast, thermal response temperature
Height can be used for variously-shaped substrate, and super stretchable, is adapted to physical activity such as muscle stretch etc., is hopeful
Substitute traditional thermo electric material extensive use.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of super stretchable graphene Electric radiant Heating Film and its
Preparation method.
The purpose of the present invention is what is be achieved through the following technical solutions:A kind of super stretchable graphene Electric radiant Heating Film, institute
It states Electric radiant Heating Film to be woven by graphene fibre electroheating, the graphene fibre electroheating has pair being made of graphene nanometer sheet
Archimedian screw structure, piece interlamellar spacing are 0.3~0.35nm, and the carbon-to-oxygen ratio of fiber is 52.66~98, conductivity 0.8-
2.36×106S/m, elongation at break 30%-220%.
A kind of preparation method of super stretchable graphene Electric radiant Heating Film, its steps are as follows:
(1) graphene oxide membrane that thickness is 0.8~50 μm is prepared;
(2) it is warming up to 500-800 DEG C with the rate of 0.1-1 DEG C/min, keeps the temperature 0.5-2h, then with the rate of 1-3 DEG C/min
It is warming up to 1000-1300 DEG C, keeps the temperature 0.5-3h, is then warming up to 2000-3000 DEG C with the rate of 5-8 DEG C/min, keeps the temperature 0.5-
4h;
(3) graphene film after being heat-treated step 3 is cut into graphene strips, graphene strips one end is fixed, the other end
It is connected with the rotor that rotating speed is 250-300 turns/min, after radially winding 1~5min, obtains the graphene fiber of quick response;
(4) graphene fiber for the ultrafast electro-thermal response that step 3 obtains is woven into Electric radiant Heating Film.
Further, the aqueous solution of graphene oxide is passed through vacuum filtration by the graphene oxide membrane in the step (1)
Method, spin-coating method, one kind in the methods of spray coating method are prepared.
Further, the graphene oxide is obtained by natural graphite chemical oxidation stripping method.
The present invention has advantageous effect in that compared with prior art:
1. the raw material of graphene is easy to get extensively, of low cost.
2. preparation process is simple, size is controllable.
3. graphene Electric radiant Heating Film has the rate of heat addition and rate of temperature fall of superelevation, the temperature-responsive of superelevation, and operating voltage
It is relatively low, it can be used for human body, used as human body electrothermal cloth, and (single elongation at break reaches due to that can draw high performance
150%) physical activity, such as muscle stretch, are adapted in use, therefore can extensively be answered as intelligent electric-heating material
With.
Description of the drawings
Fig. 1 is the schematic diagram radially wound.
Fig. 2 is that graphene Electric radiant Heating Film generates fast electric heating response gray-scale map;
Fig. 3 is the infrared imaging gray-scale map of the unstretched 1. fibers different degrees of with stretching of 4.1V.
Fig. 4 is the sectional view of fiber, and lower right insertion is double Archimedian screw structural schematic diagrams.
Specific implementation mode
As shown in figure 4, a kind of super stretchable graphene Electric radiant Heating Film of the present invention, the Electric radiant Heating Film are fine by graphene electric heating
Dimension weaves, and the graphene fibre electroheating has the double Archimedian screw structure (structures being made of graphene nanometer sheet
Can refer to document Biscrolling Nanotube Sheets andFunctional Guests into Yarns), piece interlayer
It is 52.66~98 away from the carbon-to-oxygen ratio for 0.3~0.34nm, fiber, conductivity is 0.8-2.36 × 106S/m, elongation at break are
30%-220%.Fig. 2 is the graphene electrothermal membrane infrared image that the present invention is prepared, it can be seen from the figure that Electric radiant Heating Film
Uniformity of temperature profile, and electric heating speed is fast, it is red after being stretched at 4.1V after Fig. 3 is the fiber extraction in Electric radiant Heating Film
Outer image, it can be seen from the figure that the graphene fiber after stretching still has excellent electric heating property, Temperature Distribution equal
It is even.
A kind of super stretchable highly conductive graphene fiber and preparation method thereof of the present invention, steps are as follows:
(1) graphene oxide is obtained by natural graphite chemical oxidation stripping method, is configured to graphene oxide water solution, made
The graphene oxide membrane that standby thickness is 0.5~50 μm;
(2) it is warming up to 500-800 DEG C with the rate of 0.1-1 DEG C/min, keeps the temperature 0.5-2h, then with the rate of 1-3 DEG C/min
It is warming up to 1000-1300 DEG C, keeps the temperature 0.5-3h, is then warming up to 2000-3000 DEG C with the rate of 5-8 DEG C/min, keeps the temperature 0.5-
4h;
(3) graphene film after being heat-treated step 3 is cut into graphene strips, graphene strips one end is fixed, the other end
Being connected with the rotor that rotating speed is 250-300 turns/min, (one end is fixed, and the other end constantly rotates under rotor drive, is similar to and rubs with the hands
The rope made of hemp, as shown in Figure 1), after radially winding 1~5min, obtain graphene fiber (the safe voltage 0.5V-5V of quick response
The lower quick response realized to 30 DEG C -420 DEG C of high temperature).
(4) graphene fiber for the ultrafast electro-thermal response that step 3 obtains is woven into Electric radiant Heating Film.
Compared with traditional heating element nichrome etc., graphene fiber can within a short period of time be realized to high temperature
Quick response, the reason is that the thermal capacitance very little of graphene, and also very little, the heat of generation cannot largely assemble and generate heat thermal mass
It dissipates, after high-temperature process, a large amount of oxygen-containing functional group is removed, and conjugated structure is restored, and electric conductivity obtains very big
Raising.Further pass through winding so that the internal voids of graphene fiber are gradually extruded, and graphene fiber has close
Winding-structure, therefore resistance becomes smaller, so that graphene fiber has better electrocaloric effect.Under identical voltage, rise
Warm rate and saturation temperature are all significantly increased.
On the other hand, the graphene film composition helical structure but also strip is wound, causes graphene fiber to have super
Tensility.In drawing process, the multilayered fold that graphene film generates after high-temperature process during mechanical compaction is gradual
It is stretched out, when pulling force continues to increase, serpentine graphene fiber structure is gradually opened.The knot introduced during wound membrane
Structure defect is broken under stress concentration effect, and serpentine graphene fiber starts gradually to be broken, under a stretching force,
The graphene film of different layers is gradually hauled out, and the flake graphite alkene in graphene film is also successively hauled out, so this roll up layer by layer
Graphene fiber around structure has super stretchable property.Therefore, the graphene woven by above-mentioned graphene fiber
Electric radiant Heating Film has the rate of heat addition and rate of temperature fall of superelevation, the temperature-responsive of superelevation, and operating voltage is relatively low, can be used for people
Body is used as human body electrothermal cloth, and due to that can draw high performance (single elongation at break reaches 150%), is drawing high state
Under, good electric heating property can be still kept, physical activity, such as muscle stretch are suitable for.
Graphene oxide membrane in the step (1) can be by vacuum filtration method, in the methods of spin-coating method or spray coating method
One kind be prepared.
Present aspect is described further with reference to embodiment.
Embodiment 1:A kind of preparation method of super stretchable highly conductive graphene fiber of the present invention, steps are as follows:
(1) graphene oxide is obtained by natural graphite chemical oxidation stripping method, prepares the oxidation that thickness is 0.8~50 μm
Graphene film;
(2) graphene oxide membrane that thickness prepared by step 1 is 0.8~50 μm, according to mode shown in 1~table of table 3
It is heat-treated, obtains graphene film.
(3) by step 2, treated that graphene film is cut into graphene strips, and graphene strips one end is fixed, the other end with
The rotor that rotating speed is 260 turns/min is connected, and radially (one end is fixed, and the other end constantly turns under rotor drive after winding 3min
It is dynamic, similar to making cord, as shown in Figure 2), the electric property for each product that different heat treatment mode obtains is shown in Table 1~table 3.
Graphene oxide membrane wherein in step (1) can be by vacuum filtration method, in the methods of spin-coating method or spray coating method
One kind be prepared.
Table 1
Table 2
Table 3
As can be seen that the stretching electric heating property of this material is mainly repaiied by internal oxidation graphene film structure from 1~table of table 3
Multiple situation, i.e., functional group fall off and high temperature under the reparation of carbon conjugated structure determine.
In table 1, by comparing A1 B1 C1 D1 E1, the temperature of A1 is too low, is not enough to remove most of degradable official
It can roll into a ball, cause gas in second step pyroprocess largely quickly to generate, tear lamellar structure at high temperature;E1 temperature is excessively high, production
Angry body is too fast, can largely tear material internal structure, and material mechanical performance and electric property both can be made to be deteriorated.It has only
At a temperature of B1, C1, D1, functional group can be slow and thoroughly removes, to ensure that material has efficient stretching electro-thermal response performance.
By comparing C1 F1 G1 H1, F1 heating rates are too low, gas release it is excessively slow;H1 temperature-rise periods are too fast, and gas discharged
Soon, material internal structure is torn, is unfavorable for forming transmission channel.By comparing C1 I1 J1 K1 L1 M1, I1 soaking time mistakes
It is short, it cannot be guaranteed that the degradation of most of functional group so that materials conductive performance is deteriorated;M1 insulating processes are long, can absorb stove
The tar of the inside is unfavorable for the promotion of performance.Due to avoiding with middle adverse conditions, performance has obtained very by J1, K1, L1, M1
Big raising.
In table 2, by comparing A2 B2 C2 D2 E2, A2 heating rates are too low, seriously affect elongation at break and electric heating
Performance.E2 heating rates are excessively high, can tear graphene interlayer structure so that degradation.Have the heating rate of B2, C2, D2 only
Under, it just capable can not only ensure structure but also ensure the electric conductivity of graphene.By comparing C2 F2 G2 H2, F2 temperature is too low, makes
Obtaining stable functional group cannot be sufficiently disengaged from, and discharge gas, destruction internal structure in follow-up graphited transition easy in the process;
By comparing C2 I2 J2 K2 L2 M2, I2 soaking times are too short, and stable functional group cannot fully fall off;M2 overlong times,
Graphene film is easy tar adsorption, is unfavorable for the promotion of graphene film performance;And can both it ensure under the conditions of C2, J2, K2, M2 steady
Determine fully falling off for functional group, and is avoided that the puzzlement of tar.
In table 3, by comparing A3 B3 C3 D3 E3, A3 heating rates are too low, and most stabilising functional group falls off excessively slow, no
Conducive to the formation of conductive network, to influence the electric heating property of grapheme material;E3 temperature-rise periods are too fast, gas release and height
Temperature expansion is too fast, is easily destroyed structure.Only in the case of B3, C3, D3, shape that the graphene film of conductive network could be stablized
At the structure on graphene could be repaired slowly.By comparing C3 F3 G3 H3 I3, F3 outlet temperatures are too low, graphene
Structure repair is incomplete, so mechanics and electric property are all very poor;I3 outlet temperatures are excessively high, and graphene can be vaporized;C3、
It could not only ensure the reparation of graphene-structured at a temperature of G3, H3, but also will not be vaporized.By comparing C3 J3 K3 L3
M3, J3 soaking time are too low, and graphene-structured cannot be repaired fully, and M3 soaking times are long, can also to adsorb in furnace body
Tar influences the performance of grapheme material.
Claims (4)
1. a kind of preparation method of super stretchable graphene Electric radiant Heating Film, which is characterized in that its steps is as follows:
(1)Prepare the graphene oxide membrane that thickness is 0.8 ~ 50 μm;
(2)With 0.1-1oThe rate of C/min is warming up to 500-800 oC keeps the temperature 0.5-2h, then with 1-3 oThe rate of C/min heats up
To 1000-1300oC keeps the temperature 0.5-3h, then with 5-8 oThe rate of C/min is warming up to 2000-3000 oC keeps the temperature 0.5-4h;
(3)By step 2 be heat-treated after graphene film be cut into graphene strips, graphene strips one end is fixed, the other end with turn
The rotor that speed is 250-300 turns/min is connected, and after radially winding 1~5min, obtains the graphene fiber of quick response;
(4)The graphene fiber for the ultrafast electro-thermal response that step 3 obtains is woven into Electric radiant Heating Film.
2. according to the method described in claim 1, it is characterized in that, the step(1)In graphene oxide membrane be that will aoxidize
The aqueous solution of graphene is prepared by one kind in vacuum filtration method, spin-coating method, spray coating method.
3. according to the method described in claim 2, it is characterized in that, the graphene oxide is shelled by natural graphite chemical oxidation
It is obtained from method.
4. the super stretchable graphene Electric radiant Heating Film that a kind of method as described in claim 1 is prepared, which is characterized in that institute
It states Electric radiant Heating Film to be woven by graphene fibre electroheating, the graphene fibre electroheating has pair being made of graphene nanometer sheet
Archimedian screw structure, piece interlamellar spacing are 0.3 ~ 0.35nm, and the carbon-to-oxygen ratio of fiber is 52.66 ~ 98, conductivity 0.8-2.36
×106S/m, elongation at break 30%-220%.
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CN112291868B (en) * | 2020-09-14 | 2021-12-14 | 兰州大学 | Self-annealing graphene self-supporting high-temperature electrothermal film and preparation method thereof |
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Effective date of registration: 20190904 Address after: 313199 Room 830, 8th Floor, Changxing World Trade Building, 1278 Mingzhu Road, Changxing Economic Development Zone, Huzhou City, Zhejiang Province Patentee after: Changxin de Technology Co., Ltd. Address before: 310058 Xihu District, Zhejiang, Yuhang Tong Road, No. 866, No. Patentee before: Zhejiang University |